Active radiation ray curable, solar radiation blocking resin compositions and films coated therewith

ABSTRACT

This invention provides a resin composition which is cured by active radiation rays, shows less absorption in the visible light region, has solar radiation blocking ability and is excellent in scratch resistance, and a film coated with the resin composition. Said resin composition comprises solar radiation absorbable fine particles of a metal oxide such as zinc antimonate anhydride, tin oxide, ATO (antimony doped tin oxide), ITO (tin doped indium oxide) or the like and an active radiation ray polymerizable (meth)acrylate having a (meth)acryloyl group, and a coating obtained therefrom has excellent paint film hardness and scratch resistance.

TECHNICAL FIELD

This invention relates to a solar radiation(heat wave or heat ray)blocking resin composition curable with active radiation rays such asultraviolet rays and the like, which comprises solar radiationabsorbable fine particles of an inorganic metal having a primaryparticle size of 0.5 μm or less and an active radiation raypolymerizable (meth)acrylate having a (meth)acryloyl group, and toscratch resistable films coated therewith.

Solar radiation blocking materials have been extensively researched anddeveloped, particularly in recent years and can be used inphoto-sensitive materials to semiconductor laser beam or the like rayshaving a wave length of the near infrared ray region as the lightsource, in information recording materials such as recording materialsfor photodisc and the like and in windows of buildings, car windows andthe like as infrared cutting filters or solar radiation blocking films.

BACKGROUND ART

Chrome, cobalt complex salt thiol nickel complexes, anthraquinonederivatives and the like are known in the prior art as near infrared rayabsorbable, light transmitting materials. Also known is a solarradiation reflecting film in which aluminum, copper or the like metal isvacuum-deposited on one surface of a polyethylene terephthalate film.Since such an infrared rays reflecting film well transmits visible raysbut reflects near infrared--infrared rays, when applied to a glass ofwindow or the like opening part of buildings, it exerts daylightcontrolling and heat insulating effects by reflecting solar radiation ofthe sun light or heat radiation from the interior of the room, keepingits transparency. Transparent, thermal insulation films having suchcharacteristics are applied to windows of buildings,freezer-refrigerator show cases, thermal insulating surfaces, carwindows and the like and useful for example in improving dwellingenvironment and saving energy.

However, solar radiation blocking materials of the prior art, when madesolely of organic materials, have a disadvantage in that their initialproperties are deteriorated as the environmental conditions change orwith the lapse of time, due to their poor durability (weather resistanceor the like). On the other hand, those which are made of complexmaterials have good durability, but they not only absorb rays of nearinfrared region spectra but also absorb visible region spectra and thecompounds themselves are strongly colored, and thus their applicationsare limited.

Also, solar radiation reflecting films of the prior art reflect not onlyinfrared rays but also visible rays by the metal deposited, thus posinga fatal disadvantage in that the interior of a room becomes dark whenthey are applied to window glass and the like. In addition, since alarge apparatus is necessary to form such a deposited layer of metals,their production cost becomes high and their general use as finalproducts therefore becomes limited.

In order to form a layer or coat of solar radiation absorbents, thesolar radiation absorbing agents must be uniformly dispersed in resins.As binders of the resin, acrylic resin, polyester resin, alkyd resin,polyurethane resin, epoxy resin, amino resin, vinyl resin or the likethermoplastic resins are generally used. However, these resins to beused as the binder are apt to get flaws due to poor scratch resistanceof the coated layer. In order to improve scratch resistance of thesefilms to a practical level, it is desirable to carry out a hard coatingtreatment on the outer surface of reflecting film. However, such aprocess in which a solar radiation absorbing material is coated and thenits outer surface is again subjected to hard coating leads to highercost and poorer general use.

DISCLOSURE OF THE INVENTION

The inventors of the present invention have conducted intensive studieson a solar radiation blocking material which has an absorption at thenear infrared--far infrared region, less coloring and excellentdurability, and found that a solar radiation blocking resin compositioncurable with active radiation rays such as ultraviolet rays and thelike, from which a coated film having excellent scratch resistance canbe obtained by curing through the irradiation of ultraviolet rays andthe like and yet by a single coating, can be obtained by dispersing fineparticles of an inorganic metal, particularly fine particles of a metaloxide, having a primary particle size of 0.5 μm or less, preferably 0.1μm or less, in a resin which is curable with ultraviolet rays and thelike active radiation rays, thus resulting in the accomplishment of thepresent invention.

The present invention relates to a solar radiation blocking resincomposition which is curable with active radiation rays such asultraviolet rays and the like and gives excellent scratch resistance,which comprises solar radiation absorbable fine particles of aninorganic metal having a primary particle size of 0.5 μm or less and, asits binder, an active radiation ray polymerizable (meth)acrylate havinga (meth)acryloyl group, and to films coated therewith.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing spectral characteristics of the films (a) to(c) obtained by coating the resin composition of the present invention(Example 3) on polyester films and of an un-coated polyester film (d).

FIG. 2 is a graph showing solar radiation blocking characteristics ofthe polyester film (c) coated with the resin composition of the presentinvention.

FIG. 3 is a graph showing spectral characteristics of the film of thepresent invention (Example 8).

FIG. 4 is a graph showing spectral characteristics of the films of thepresent invention (Examples 3 and 10) and of the film of ComparativeExample 5.

FIG. 5 is a graph showing spectral characteristics of the film of thepresent invention (Example 13) and of an un-coated transparent polyesterfilm.

BEST MODE OF CARRYING OUT THE INVENTION

Examples of the metal having solar radiation absorption ability includetitanium oxide, zinc oxide, vanadium oxide, indium oxide, tin oxide,antimony oxide, zinc sulfide and the like, and tin oxide, ATO (tin oxideantimony doped), ITO (tin oxide indium doped), zinc antimonate anhydrideand the like metal oxides are particularly effective.

ATO can be produced for example by a method described in Japanese PatentApplication Kokai No. 58-117228(1983) or Japanese Patent ApplicationKokai No. 6-262717(1994), and ITO for example by a method disclosed inJapanese Patent Application Kokai No. 63-11519(1988).

In addition, zinc antimonate anhydride sol (for example, Cellunax CX-Z(ZnSb₂ O₆) manufactured by Nissan Chemical Industries) can also be usedsuitably in the present invention as a metal oxide having infrared rayabsorption ability. Since zinc antimonate anhydride has an absorption atthe ultraviolet region having shorter wave length than the visibleregion, its effect to improve light resistance can also be expected. Inaddition, since zinc antimonate anhydride has a function as a flameretarding agent derived from antimony pentaoxide, films obtained by itscoating have flame resistance. Antimony pentaoxide can be produced forexample by a method disclosed in Japanese Patent Publication Kokoku No.6-17234(1994) or Japanese Patent Publication Kokoku No. 7-29773(1995),and zinc antimonate anhydride can be produced for example by a methoddisclosed in Japanese Patent Application Kokai No. 6-219743(1994). Fineparticles of the zinc antimonate anhydride can be obtained for exampleby mixing a zinc compound with colloidal antimony oxide, drying themixture and then baking it at a high temperature.

It is desirable that these metal oxides are prepared in such a form thatthey can be dispersed in organic solvents. Also, in order to form ametal oxide-containing film which has less absorption at visible raysregion and is transparent, it is necessary to make it into a fineparticle having a primary particle size of 0.5 μm or less, preferably0.1 μm or less. Amount of the solar radiation absorbable inorganic metalcontained in the resin composition of the present invention can be setto any values depending on the required solar radiation blockingefficiency, but these particles should be dispersed stably in the resinwithout aggregation.

The active energy ray polymerizable (meth)acrylate to be used in thepresent invention can be selected from (meth)acrylates which have atleast one (meth)acryloyl group in the molecule and are curable withultraviolet beams or electron beams, which may be used alone or as amixture. Illustrative examples of the (meth)acrylate include, though notparticularly limited to, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl(meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate,2-ethylhexyl (meth)acrylate, stearyl acrylate, 2-ethylhexylcarbitolacrylate, ωcarboxypolycaprolactone monoacrylate, acryloyloxyethylicacid, acrylic acid dimer, lauryl (meth)acrylate, 2-methoxyethylacrylate, butoxyethyl acrylate, ethoxyethoxyethyl acrylate,methoxytriethylene glycol acrylate, methoxypolyethylene glycol acrylate,stearyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl(meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl acrylate,benzyl acrylate, phenyl glycidyl ether epoxyacrylate, phenoxyethyl(meth)acrylate, phenoxy(poly)ethylene glycol acrylate, nonylphenolethoxylated acrylate, acryloyloxyethylphthalic acid, tribromophenylacrylate, tribromophenol ethoxylated (meth)acrylate, methylmethacrylate, tribromophenyl methacrylate, methacryloyloxyethylic acid,methacryloyloxyethylmaleic acid, methacryloyloxyethylhexahydrophthalicacid, methacryloyloxyethylphthalic acid, polyethylene glycol(meth)acrylate, polypropylene glycol (meth)acrylate, β-carboxyethylacrylate, N-methylol acrylamide, N-methoxymethyl acrylamide,N-ethoxymethyl acrylamide, N-n-butoxymethyl acrylamide, t-butylacrylamide sulfonic acid, vinyl stearate, N-methyl. acrylamide,N-dimethyl acrylamide, N-dimethylaminoethyl (meth)acrylate,N-dimethylaminopropyl acrylamide, acryloyl morpholine, glycidylmethacrylate, n-butyl methacrylate, ethyl methacrylate, allylmethacrylate, cetyl methacrylate, pentadecyl methacrylate,methoxypolyethylene glycol (meth)acrylate, diethylaminoethyl(meth)acrylate, methacryloyloxyethylsuccinic acid, hexanedioldiacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate,polyethylene glycol diacrylate, polypropylene glycol diacrylate,neopentyl hydroxypivalic acid ester, pentaerythritol diacrylatemonostearate, glycol diacrylate, 2-hydroxyethylmethacryloyl phosphate,bisphenol A ethylene glycol adduct acrylate, bisphenol F ethylene glycoladduct acrylate, tricyclodecanemethanol diacrylate, trishydroxyethylisocyanurate diacrylate, 2-hydroxy-1-acryloxy-3-methacryloxypropane,trimethylolpropane triacrylate, trimethylolpropane ethylene glycoladduct triacrylate, trimethylolpropane propylene glycol adducttriacrylate, pentaerythritol triacrylate, trisacryloyloxyethylphosphate, trishydroxyethyl isocyanurate triacrylate, modifiedε-caprolactone triacrylate, trimethylolpropane ethoxy triacrylate,glycerol propylene glycol adduct triacrylate, pentaerythritoltetraacrylate, pentaerythritol ethylene glycol adduct tetraacrylate,ditrimethylolpropane tetraacrylate, dipentaerythritolhexa(penta)acrylate, dipentaerythritolmonohydroxy pentaacrylate,urethane acrylate, epoxy acrylate, polyester acrylate, unsaturatedpolyester acrylate and the like. These compounds may be used alone or asa mixture thereof, of which a multifunctional (meth)acrylate monomer oroligomer having two or more (meth)acryloyl groups in one molecule ispreferred, because its coat film after polymerization is hard and hasexcellent scratch resistance. Ratio of these active energy raypolymerizable (meth)acrylate to the resin component in the heat waveblocking resin composition is preferably 10% by weight or more and 98%by weight or less, more preferably from 30 to 80% by weight.

In order to improve adhesiveness with films or compatibility of fineparticles of an inorganic metal with the ultraviolet ray curable resin,an acrylic resin, a polyester resin, a butyral resin, a urethane resinor the like polymer may be used as a binder component which can be addedas occasion demands in addition to the active energy ray polymerizable(meth)acrylate having (meth)acryloyl group. For example, Viron (apolyester resin manufactured by Toyobo Co.) can be used as the polyesterresin, and Eslex manufactured by Sekisui Chemical Co. as the butyralresin. Particularly, a polymer having hydroxy group (a polyester resin,a butyral resin or the like for example, though not particularly limitedto) is preferred, because dispersibility of fine particles of aninorganic metal becomes excellent and it simultaneously exerts actionsto improve adhesiveness of ink and reduce shrinking of coated films.Ratio of this additional polymer to the resin component in thecomposition is preferably 3% by weight or more and 50% by weight orless, more preferably 20% by weight or less. When the amount of thispolymer is too much, scratch resistance of the obtained film is reduced,so that it cannot be used in an application in which the coated sidefaces outside.

In order to disperse the fine particles of an inorganic metal thoroughlyin the ultraviolet ray curable type resin, a dispersing agent may beadded as occasion demands. Examples of the dispersing agent includeanionic surface active agents of sulfuric ester, carboxylic acid,polycarboxylic acid and the like systems, cationic surface active agentssuch as a quaternary salt of a higher aliphatic amine and the like,nonionic surface active agents such as a higher fatty acid polyethyleneglycol ester and the like, silicon base surface active agents, fluorinebase surface active agents and high molecular active agents having amideester bonds. Of these agents, when the inorganic metal is tin oxide,vanadium oxide, ATO, ITO or the like, dispersing agents of carboxylicacid and polycarboxylic acid systems are particularly preferred, andtheir examples include carboxylic acid base surface active agents suchas R-COOH, RSO₂ NHCH₂ COOH, RSCH₂ COOH, RSOCH₂ COOH, RCH₂ COOH, RCH(SO₃H)COOH and the like sulfonic acid-carboxylic acid systems (R representsa saturated or unsaturated alkyl group having 10 to 20 carbon atoms) andpolycarboxylic acid system surface active agents having a repeating unitof --CH₂ --CH(COOH)--, CH₂ CH(CH₂ COOH)--CH(Ph)--CH₂ --,--CH(COOH)--CH(COOH)--C(CH₃)₂ --CH₂ --, --CH₂ --CH(CH₂ COOH)-- or thelike. Their illustrative examples include Floren AF-405, G-685, G-820and the like (manufactured by Kyoei-sha Yushi Co.).

When the inorganic metal is zinc antimonate anhydride or its sol,various surface active agents can be used as the dispersing agent, andtheir preferred examples include a higher aliphatic amine quaternarysalt, a polyethylene glycol alkylamine and the like cationic surfaceactive agents, a higher fatty acid polyethylene glycol ester and thelike nonionic surface active agents, amphoteric surface active agents,silicon base surface active agents, fluorine base surface active agentsand high molecular active agents having amide ester bonds. Thedispersing agent may be added in an amount of preferably 0.1% by weightor more and 15% by weight or less based on the total weight of the fineparticles of an inorganic metal.

The resin composition of the present invention may further contain acompound having maximum absorption wave length at the near infraredregion of 1,200 nm or less, such as a specified amino compoundrepresented by a formula (1): ##STR1## (in the formula, R represents Hor an alkyl group having 1 to 12 carbon atoms, X represents SbF₆, ClO₄,Cl or Br, and each of m and n is 1 or 2).

It is said in general that the thermal energy contained in the sun lightis divided into two almost equal parts of the visible light region andthe infrared region having longer wave length. The present inventionintends to absorb and block thermal energy of the infrared regionefficiently, while improving visible light transmittance as large aspossible. According to the present invention, it was found thatexcellent durability and effective absorption of solar radiationspectrum can be obtained when fine particles of an inorganic metalhaving thermal absorption ability are combined with a compound havingmaximum absorption wave length at the near infrared region of 1,200 nmor less, such as the amino compound of formula (1), so that moreexcellent solar radiation absorption ability is exerted and the visiblelight transmittance is also improved. A substance absorbing spectrathrough a broad range has not been found yet. At the same time, a coatedfilm having excellent scratch resistance and durability can be formedefficiently, by the use of an active radiation ray curable type (meth)acrylate as a resin binding these solar radiation absorbing agents.

Typical examples of the compound having maximum absorption wave lengthat the near infrared region of 1,200 nm or less, to be used in thepresent invention, are amino compounds represented by the structure offormula (1) which have a maximum absorption wave length of about 750 nmor more and 1,200 nm or less. These compounds may be used alone or as amixture as occasion demands. The amino compound can be applied to thepresent invention when made into fine particles of 0.5 μm or less,preferably 0.1 μm or less, in common with the case of the metal havingsolar radiation absorption ability, but it is more desirable to use itby dissolving in an organic solvent in view of its effects and easypreparation. The amino compound can be synthesized in accordance withthe method disclosed in U.S. Pat. Nos. 3,484,467, 3,637,7769 or thelike, and its examples include hexafluoroantimonic acid salt ofbis(p-dibutylaminophenyl)-[p-N,N-bis(p-dibutylaminophenyl)aminophenyl]-aminium,N,N,N,N-tetrakis(p-dibutylaminophenyl)-1,4-benzeneiminium=dihexafluoroantimonate,N,N,N,N-tetrakis(p-dibutylaminophenyl)-1,4-benzeneiminium=diperchlorateand the like, though not particularly limited thereto. Ratio of theamino compound to the solid components of the resin composition can beselected at will depending on the required solar radiation blockingefficiency, but, in order to prevent reduction of visible raytransmittance, it may be within the range of preferably from 0.1% byweight to 50% by weight, more preferably from 0.5% by weight to 20% byweight.

The resin composition of the present invention may further contain aphthalocyanine compound represented by the following formula (2):##STR2## (in the formula, X independently represents hydrogen atom, ahalogen atom, --SR¹, --OR² or --NR³ R⁴ ; each of R¹ and R² independentlyrepresents phenyl group, benzyl group, naphthyl group, a cycloalkylgroup, an alkyl group having 1 to 20 carbon atoms or an alkoxyl group,each of which may have a substituent group; each of R³ and R⁴independently represents hydrogen atom, an alkyl group having 1 to 20carbon atoms, a cycloalkyl group or phenyl group which may have asubstituent group; a is an integer of 1 to 4; and M is non-metal (inthat case, the formula (2) means a non-metal phthalocyanine), a metal, ametal oxide or a metal halide).

According to the present invention, excellent durability and broadabsorption through wide range of solar radiation spectra can be obtainedwhen the metal fine particles having solar radiation absorption abilityare combined with the specified phthalocyanine compound, so that moreexcellent solar radiation absorption ability is exerted and, at the sametime, a coated film having excellent scratch resistance and durabilitycan be formed efficiently by the use of the active radiation ray curabletype (meth)acrylate as a resin binding these solar radiation absorbingagents.

The specified phthalocyanine compound to be used in the presentinvention is represented by the structure of formula (2) and has amaximum absorption wave length of preferably 600 nm or more, morepreferably 750 nm or more, from the viewpoint of improving visible lighttransmittance. In the formula (2), examples of the halogen atom includefluorine atom, chlorine atom, bromine atom and the like, examples of thecentral metal (M) include copper, zinc, iron, cobalt, titanium,vanadium, nickel, indium, tin and the like and examples of the metalhalide include fluorides, chlorides, bromides, iodides and the like.When (M) is non-metal, it means for example two hydrogen atoms. Thoughmany of phthalocyanine compounds are not soluble in solvents in general,those which are insoluble in solvents can be applied to the presentinvention when made into fine particles of 0.5 μm or less, preferably0.1 μm or less, in common with the case of the metal having solarradiation absorption ability, but it is more desirable from the viewpoint of easy preparation to select a phthalocyanine compound which issoluble in organic solvents. The phthalocyanine compound can besynthesized in accordance with the method disclosed for example inJapanese Patent Application Kokai No. 4-8771(1992), Japanese PatentApplication Kokai No. 5-222047(1993), Japanese Patent Application KokaiNo. 5-222302(1993), Japanese Patent Application Kokai No. 5-345861(1993)or Japanese Patent Application Kokai No. 6-25548(1994). Ratio of thephthalocyanine compound to the solid components of the resin compositioncan be selected at will depending on the required solar radiationblocking efficiency, but it may be within the range of preferably from0.1 to 30% by weight, more preferably from 0.5 to 20% by weight.

When a film (coated film) is formed by exposing the resin composition ofthe present invention to ultraviolet ray, a photopolymerizationinitiator is used, and the photopolymerization initiator is dissolved inthe resin composition in advance. As the photopolymerization initiator,any of various known compounds can be used with no particularlimitation, and its amount to be used is 0.1 to 15% by weight,preferably 0.5 to 12% by weight relative to the resin composition,because curing ability is reduced when the amount is too small whilestrength of the cured film is reduced when it is too large. Illustrativeexamples of the photopolymerization initiator include Irgacure 184,Irgacure 651 (both manufactured by Ciba-Geigy Co.), Dalocure 1173(manufactured by Merck Co.), benzophenone, methyl o-benzoylbenzoate,p-dimethyl benzoate, thioxanthone, alkylthioxanthone, amines and thelike. Such initiators are not particularly required when curingpolymerization is carried out using electron beams.

In addition, it is possible to add various slipping agents for thepurpose of improving slipping properties of the surface of coated films,or to add an antifoaming agent with the aim of controlling bubbles whichare generated when the composition is coated. Also, as occasion demands,various organic solvents such as toluene, xylene, ethyl acetate,alcohols, ketones and the like aromatic or aliphatic organic solventsmay be added.

Production of the resin composition of the present invention and coatingof the composition on films can be effected for example by the followingmethods.

A dispersion prepared in advance by dispersing fine particles of aninorganic metal of 0.5 μm or less in an organic solvent is mixed with adispersion or solution of the specified amino compound or phthalocyaninecompound represented by the aforementioned formula (1) or (2),respectively, as occasion demands, preferably further adding a smallamount of a dispersing agent and a polymer to the mixture to effectstabilization of the dispersion. Thereafter, the solar radiationblocking resin composition of interest is obtained by adding one or aplurality of (meth)acrylate monomers or oligomers which can bepolymerized by the irradiation of active radiation rays, if necessary byfurther dissolving an initiator. At this stage, appropriate amounts of asolvent and various additives can be added as occasion demands. Theorder of mixing each of these components is not particularly limited tothe above order, with the proviso that the stabilization of the fineparticles of the metal and amino compound or phthalocyanine compound canbe achieved. The thus obtained composition is coated in one layer on atransparent film base and then active radiation rays such as ultravioletrays or electron beams are irradiated, thereby a solar radiationblocking film having markedly high visible rays transmittance andexcellent scratch resistance and solar radiation blocking efficiencybeing obtained. Alternatively, a similarly excellent solar radiationblocking film can be obtained by coating a resin composition containingfine particles of an inorganic metal and another resin compositioncontaining an amino compound or a phthalocyanine compound on a film intwo different layers or separately on both surfaces of the film. In thatcase, the amino compound or phthalocyanine compound of theaforementioned formula (1) or (2) is dispersed, preferably dissolved, inthe aforementioned (meth)acrylate containing an additional binderpolymer and/or an initiator and coated on one surface of a transparentfilm, and then a resin composition comprising fine particles of a metaland an additional binder polymer and/or the aforementioned(meth)acrylate is coated on the thus prepared layer or on the othersurface of the film. When they are coated on both surfaces of a film,one surface may be a polymer which contains an adhesive. The coating ofthe composition on a film is carried out by a usual method such asdipping, gravure coating, offset coating, roll coating, bar coating,spraying or the like method, and the solvent is evaporated with hot airafter the coating, subsequently irradiating active energy rays such aselectron beams or ultraviolet rays when the coating composition containsa (meth)acrylate, thereby effecting instant polymerization and curing ofthe solar radiation blocking composition coated on the film surface. Thepaint film to be coated may have a thickness after drying of generallyfrom 0.1 to 50 μm, preferably from 2 to 10 μm, from the viewpoint ofpreventing curling.

Examples of the film to be coated include polyester, polyethylene,polypropylene, polystyrene, polycarbonate, polyvinyl chloride,poly(meth)acryl, polyamide, polyurethane and the like, of whichpolyester is particularly preferred from the viewpoint of workabilityand strength. It is desirable that these film base materials have hightransparency, but a colored film base material can also be used asoccasion demands. Also useful are films on which metals (aluminum,chromium, copper, gold, silver and the like) are vacuum-deposited.

When the film base material is a vacuum-deposited film, it is desirablethat the visible rays transmittance is 20% or more and 90% or less,preferably 40% or more and 80% or less, in view of the balance of solarradiation blocking efficiency with visible light transmittance. Asoccasion demands, a colored deposition film base may also be used.Aluminum, copper, gold, silver, chromium or the like may be used as themetal to be deposited on the film, though not particularly limitedthereto with the proviso that it has an ability to block solarradiation. The metal deposited film can be obtained by vacuumdeposition, sputtering or the like known method. In order to protect themetal deposited on the film, it may be further coated with a resinlayer.

EXAMPLES

Next, preparation method of the resin composition of the presentinvention is described with reference to the following examples. Eachadding ratio in the examples is % by weight.

Example 1

A container equipped with a stirrer is charged with 30 parts ofdispersion of ATO (antimony doped tin oxide) having a primary particlesize of 0.1 μm or less which are suspended in toluene to a solid contentof 50%, and 6 parts of 3% toluene solution of a dispersing agent FlorenAF-405 (a polycarboxylic acid base dispersing agent manufactured byKyoei-sha Yushi Co.) is added thereto while thoroughly stirring. Withstirring, to this is further added 20 parts of toluene. While thoroughlystirring, to this is added 7 parts of a polyester resin Bylon 24SS(manufactured by Toagosei Co.) in small portions. Subsequently, to thisis added 20 parts of an ultraviolet ray curable resin dipentaerythritolhexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co.) in smallportions, while thoroughly stirring the contents. Finally, this is mixedwith 1.4 parts of a photopolymerization initiator Irgacure 184, 0.1 partof a slipping agent SH-29PA (manufactured by San Nopco Co.) and 10 partsof toluene, and the mixture is stirred until the photopolymerizationinitiator is completely dissolved, thereby obtaining an ultraviolet raycurable type solar radiation blocking resin composition (1). Thiscomposition had a solid content of 41% and a viscosity of 11.7 cps andwas dispersion-stable.

Example 2

The procedure of Example 1 was repeated, except that 6 parts of 3%solution of Floren G-820 was used as the dispersing agent, therebyobtaining a resin composition (2) having a solid content of 41% and aviscosity of 13.4 cps.

Example 3

The procedure of Example 1 was repeated, except that 10 parts of Viron24SS was used as the polyester resin, thereby obtaining a resincomposition (3) having a solid content of 41% and a viscosity of 11.5cps.

Example 4

The procedure of Example 1 was repeated, except that 7. parts of Bylon20SS was used as the polyester resin, thereby obtaining a resincomposition (4).

Example 5

The procedure of Example 1 was repeated, except that 12 parts of 3%toluene solution of Floren G-405 was used as the dispersing agent,thereby obtaining a resin composition (5).

Example 6

The procedure of Example 1 was repeated, except that 50% dispersion ofITO (tin doped indium oxide) dispersed in toluene was used as the fineparticles of an inorganic metal, thereby obtaining a resin composition(6).

Example 7

The procedure of Example 1 was repeated, except that 50% dispersion oftin oxide dispersed in toluene was used as the fine particles of aninorganic metal, thereby obtaining a resin composition (7).

Comparative Example 1

To 100 parts of 50% dispersion of ATO dispersed in toluene is added 6parts of 3% solution of Floren G-820 as the dispersing agent, followedby thoroughly stirring. This was mixed with 100 parts of the polyesterresin Bylon 20SS as a binder, and the mixture was thoroughly stirred toobtain a resin composition (8) having a solid content of 38.9%.

Comparative Example 2

To 100 parts of 50% dispersion of ATO dispersed in toluene is added 6parts of 3% solution of Floren G-820 as the dispersing agent, followedby thoroughly stirring. This was mixed with 50 parts of an acrylic resinP-5109 (manufactured by Nippon Kayaku Co.) as a binder, and the mixturewas thoroughly stirred to obtain a resin composition (9) having a solidcontent of 40.4%.

Comparative Example 3

The procedure of Comparative Example 1 was repeated, except that 50%dispersion of ITO dispersed in toluene was used, thereby obtaining aresin composition (10).

Comparative Example 4

The procedure of Comparative Example 2 was repeated, except that 50%dispersion of tin oxide dispersed in toluene was used, thereby obtaininga resin composition (11).

[Preparation of Coating Film]

(1) Each of the resin compositions obtained in Examples 1 to 7 andComparative Examples 1 to 4 was coated on a polyester film of 50 micronsin thickness using a coating bar, dried with hot air and then, in thecase of the resin composition (1) to resin composition (7), cured byexposing it to ultraviolet rays with a high pressure mercury lamp of 80W/cm at a conveyor speed of 20 m/min to obtain the coating film ofinterest. In the case of the resin compositions (8) to (11), eachcomposition which is made into a coat by hot air drying was used as acoating film sample. Scratch resistance, transparency and near infraredspectral characteristics of the thus obtained films are shown in Table1.

(2) FIG. 1 shows spectral characteristics of films (a), (b) and (c)obtained by coating the composition (3) of Example 3 in respectivecoating thicknesses of 2.7μ, 3.5μ and 4.6μ on a polyester film of 50microns in thickness, as well as of an un-coated polyester film (d). Thefilm (b) showed a visible light transmittance of 83.6% and an absorptionratio of solar radiation of 0.23. The film (c) showed a visible raystransmittance of 80.0% and a absorption ratio of solar radiation of 0.27(visible light transmittance was measured in accordance with theprocedure of JIS A 5759, and absorption ratio of solar radiation wasmeasured in accordance with the procedure of JIS R 3106).

(3) Five inner surfaces of a styrene foam container having a spacevolume of 20×20×20 cm was painted black, and the opening portion of oneof two containers obtained in this manner was covered with a transparentglass plate (1.5 mm in thickness), and that of the other container withthe same transparent glass plate but whose inner side has been laminatedwith the film (c) prepared fromthe composition of Example 3, to measuretemperature rise curves inside the containers under direct sunlight (theweather: fine weather, 26.5° C. in atmospheric temperature). The resultsare shown in FIG. 2. Smaller temperature rise means superior solarradiation blocking efficiency.

                  TABLE 1                                                         ______________________________________                                                           Physical properties of paint film                                   Dispersion                                                                              coated on PET film                                                  stability of         Scratch                                                                              Pencil                                   Composition                                                                            composition                                                                             Transparency                                                                             resistance                                                                           hardness                                 ______________________________________                                        (1)      good      transparent                                                                              OO     2 H                                      (2)      good      transparent                                                                              OO     2 H                                      (3)      good      transparent                                                                              OO     2 H                                      (4)      good      transparent                                                                              OO     2 H                                      (5)      good      transparent                                                                              OO     2 H                                      (6)      good      transparent                                                                              OO     2 H                                      (7)      good      transparent                                                                              OO     2 H                                      (8)      good      transparent                                                                              XX     B or less                                (9)      good      transparent                                                                              XX     B or less                                (10)     good      transparent                                                                              XX     B or less                                (11)     good      transparent                                                                              XX     B or less                                ______________________________________                                         OO: very good                                                                 XX: very bad                                                             

Example 8

Preparation of Composition A

A container equipped with a stirrer was charged with 50 parts of atoluene dispersion containing 50% of ATO having a primary particle sizeof 0.1 μm or less, and 7 parts of a polyester resin Bylon 24SS(manufactured by Toyobo Co.) was added in small portions to thedispersion while stirring. Subsequently, 18.5 parts of toluene and 22.4parts of an ultraviolet ray curable type monomer of dipentaerythritolhexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co.) weredissolved therein and then 2 parts of a photopolymerization initiatorIrgacure 184 was dissolved, thereby obtaining an ultraviolet ray curabletype resin composition A.

Preparation of Composition B

Six parts ofN,N,N,N-tetrakis(p-dibutylaminophenyl)-1,4-benzeneiminium=dihexafluoroantimonatewas dissolved in 60 parts of methyl ethyl ketone, subsequentlydissolving 8.8 parts of dipentaerythritol hexaacrylate and 0.7 part ofIrgacure 184, thereby obtaining an ultraviolet ray curable type resincomposition B.

The composition A was mixed with the composition B at a ratio of59.6:40.4, and the mixture was coated on a transparent polyester film toa thickness of 8.5 g/m², dried with hot air of 70° C. to evaporate thesolvent and then exposed to ultraviolet rays with a high pressuremercury lamp of 80 W/cm at a conveyor speed of 20 m/min to effectpolymerization curing of the coated film, thereby obtaining the solarradiation blocking coating film of interest.

Example 9

The composition B prepared in Example 8 was coated on a transparentpolyester film to a dried thickness of 1.81 g/m², dried with hot air of80° C. to evaporate the solvent and then exposed to ultraviolet rayswith a high pressure mercury lamp of 80 W/cm at a conveyor speed of 25m/min to effect curing of the coated film. Thereafter, the composition Awas coated thereon to a dried thickness of 6.7 g/m², dried and thenexposed to ultraviolet rays under the same conditions to effectpolymerization curing of the coated film, thereby obtaining the solarradiation blocking coating film of interest.

Example 10

Preparation of Composition C

In 50 parts of methyl ethyl ketone was dissolved 0.2 part ofN,N,N,N-tetrakis(p-dibutylaminophenyl)-1,4-benzeneiminium=dihexafluoroantimonate,subsequently mixing and dissolving 150 parts of an acrylic adhesivecontaining 80% of ethyl acetate, thereby obtaining an adhesivecomposition C.

The composition A was coated on one surface of a transparent polyesterfilm to a dried thickness of 6.7 g/m², dried with hot air of 70° C. toevaporate the solvent and then exposed to ultraviolet rays of a highpressure mercury lamp of 80 W/cm at a conveyor speed of 20 m/min toeffect curing of the paint film. The adhesive composition C containingthe amino compound was coated on the opposite surface of the film to adried thickness of 21.1 g/m² and then dried with hot air of 80° C. toobtain a solar radiation blocking coating film having an adhesive .

Comparative Example 5

The composition B alone was coated on a transparent polyester film to adry weight of 0.36 g/m², dried at 70° C. and then subjected toultraviolet ray curing in the same manner as described in Example 10 toobtain a solar radiation blocking coating film.

To be used as reference, tests were carried out on a commerciallyavailable film for car in which aluminum has been deposited on a PETfilm using a vacuum metal sputtering apparatus or another commerciallyavailable film for use in the same purpose which has been colored inblack with an organic pigment. Characteristic properties of the thusobtained films are shown in Table 2, FIG. 3 and FIG. 4.

                  TABLE 2                                                         ______________________________________                                                Amounts                                                                       of solar                                                                      radiation   Characteristic                                                    absorbents  properties when coated on                                         on PET      transparent PET film                                              film                  Absorption                                              Amino           Visible light                                                                         ratio   Scratch                                       compound ATO    transmittance                                                                         of solar                                                                              resistance                                    g/m.sup.2                                                                              g/m.sup.2                                                                            (%)     radiation                                                                             (surface)                             ______________________________________                                        Ex. 8   0.7      3.25   62.02   0.59    O                                     Ex. 9   0.7      3.25   59.99   0.59    O                                     Ex. 10  0.14     3.25   67.82   0.35    O                                     Comp. Ex. 5                                                                           0.14     --     83.42   0.18    O                                     Al deposited                                                                          --       --     30.40   0.40    X                                     film                                                                          Colored film                                                                          --       --     21.02   0.35    X                                     ______________________________________                                         Visible light transmittance was measured in accordance with the procedure     of JIS A 5759.                                                                Absorption ratio of solar radiation was measured in accordance with the       procedure of JIS R 3106.                                                      (Absorption ratio of solar radiation having larger value means superior       solar radiation blocking efficiency.)                                         Scratch resistance was measured using steel wool # 0000 under a load of       200 g with 20 reciprocals.                                                    O: completely no scratches                                                    X: presence of scratches                                                 

As shown in FIG. 3 and FIG. 4, a solar radiation blocking film havingits absorption spectrum broadly ranging from the near infrared to farinfrared can be obtained when an amino compound having its absorptiononly at the near infrared region is combined with a metal having itsabsorption at the far infrared region. A material which absorbs solarradiation within such a broad range of spectrum has not been found yet.

Example 11

A container equipped with a stirrer was charged with 50 parts of toluenedispersion containing 50% of ATO having a primary particle size of 0.1μm or less, and 6 parts of toluene solution containing 3% of adispersing agent Floren AF-405 (a polycarboxylic acid base dispersingagent manufactured by Kyoei-sha Yushi Co.) was added thereto whilethoroughly stirring. Next, 13.5 parts of a toluene solution prepared bydissolving 1 part of a toluene-soluble phthalocyanine compound (EX Color803K, manufactured by Nippon Shokubai Co.) was added and then, whilecontinuing the stirring, 7 parts of a polyester resin Bylon 24SS(manufactured by Toyobo Co.) was added and dissolved in small portions.Subsequently, 21.5 parts of an ultraviolet ray curable type monomer ofdipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by NipponKayaku Co.) and 2 parts of a photopolymerization initiator Irgacure 184were added thereto and dissolved therein in that order, therebyobtaining an ultraviolet ray curable type, solar radiation blockingresin composition (12). This composition had a solid content of 51.5%and a viscosity of 15 cps and the dispersibility was stable.

Example 12

In Example 11, 14.5 parts of toluene solution containing 2 parts of EXColor 803K, namely doubled amount of the phthalocyanine compound, wasused and the amount of dipentaerythritol hexaacrylate was changed to20.5 parts in order to adjust the solid content, and the procedure ofExample 11 was repeated to obtain a solar radiation blocking resincomposition (13). In common with the case of Example 11, thiscomposition had a solid content of 51.5% and a viscosity of 16 cps andthe dispersibility was stable.

Comparative Example 6

A solar radiation blocking resin composition (14) containing no metalfine particles of ATO but comprising a phthalocyanine compound only wasobtained in the following manner. A container equipped with a stirrerwas charged with 20 parts of toluene, in which, while thoroughlystirring, was subsequently dissolved 0.3 part of a phthalocyaninecompound EX Color 803K. Subsequently, 19 parts of dipentaerythritolhexaacrylate and 1 part of a photopolymerization initiator Irgacure 184were added thereto and completely dissolved therein in that order,thereby obtaining an ultraviolet ray curable type solar radiationblocking resin composition.

Comparative Example 7

A solar radiation blocking resin composition (15) comprising aphthalocyanine compound only was obtained in the following manner byrepeating the procedure of Comparative Example 6, except that the amountof the phthalocyanine compound was doubled. A container equipped with astirrer was charged with 20 parts of toluene, in which, while thoroughlystirring, was subsequently dissolved 0.6 part of the phthalocyaninecompound EX Color 803K. Subsequently, 18.7 parts of dipentaerythritolhexaacrylate and 1 part of the photopolymerization initiator Irgacure184 were added thereto and completely dissolved therein in that order,thereby obtaining an ultraviolet ray curable type, solar radiationblocking resin composition.

[Preparation of coating film]

Each of the solar radiation blocking resin compositions obtained inExamples 11 and 12 was coated on a transparent polyester film of 50 μmin thickness using a wire bar in such an amount that the applied amountof the solid contents became 6.7 g/m², and in the same manner, each ofthe compositions of Comparative Example 6 and 7 was coated using a wirebar to an application amount of 8.8 g/m², and the thus coated films weredried with hot air of 80° C. to evaporate the solvent and then exposedto a high pressure mercury lamp of 80 W/cm at a conveyor speed of 20m/min to effect polymerization curing of the films, thereby obtainingthe solar radiation blocking coating films of interest. Also, to be usedas reference, a commercially available film for car windows in whichaluminum has been deposited on a PET film using a vacuum metalsputtering apparatus and another commercially available film for use inthe same purpose which has been colored in black with an organic pigmentwere subjected to the tests. Characteristic properties of the thusobtained films are shown in Table 3.

                  TABLE 3                                                         ______________________________________                                                Amounts                                                                       of solar                                                                      radiation                                                                     absorbents  Characteristic properties when                                    on PET      coated on transparent PET film                                    film                  Absorption                                              Phthalo-        Visible light                                                                         ratio   Scratch                                       cyanine  ATO    transmittance                                                                         of solar                                                                              resistance                                    g/m.sup.2                                                                              g/m.sup.2                                                                            (%)     radiation                                                                             (surface)                             ______________________________________                                        Ex. 11  0.13     3.25   62.03   0.43    O                                     Ex. 12  0.26     3.25   49.87   0.55    O                                     Comp. Ex. 6                                                                           0.13     --     68.60   0.24    O                                     Comp. Ex. 7                                                                           0.26     --     55.45   0.37    O                                     Al deposited                                                                          --       --     30.40   0.40    X                                     film                                                                          Colored film                                                                          --       --     21.02   0.35    X                                     ______________________________________                                         Visible light transmittance was measured in accordance with the procedure     of JIS A 5759.                                                                Absorption ratio of solar radiation was measured in accordance with the       procedure of JIS R 3106.                                                      (Absorption ratio of solar radiation having larger value means superior       solar radiation blocking efficiency.)                                         Scratch resistance was measured using steel wool # 0000 under a load of       200 g with 20 reciprocals.                                                    O: completely no scratches                                                    X: presence of scratches                                                 

As is evident from Table 3, visible light transmittance values ofExamples 11 and 12 are close to those of Comparative Examples 6 and 7,but values of the absorption ratio of solar radiation which representactual heat wave blocking capacity are considerably larger than those ofComparative Examples 6 and 7, so that the films of the invention areexcellent in solar radiation blocking efficiency. This indicates that,at the same visible light transmittance, the solar radiation blockingefficiency is synergistically improved in combination of the specifiedphthalocyanine compound with ATO (an example of the inorganic metal). Inaddition, in comparison with the deposition and colored films which arecommercially available generally as solar radiation cutting films andused herein as reference, the films of Examples 11 and 12 can show muchhigher solar radiation blocking efficiency while keeping high visiblelight transmittance.

Example 13

Preparation of Solution (D)

A container equipped with a stirrer was charged with 50 parts ofmethanol solution containing 40% of sol of zinc antimonate anhydride(ZnSb₂ O₆) having a particle size of 0.1 μm or less, and 3.5 parts of adispersing agent Pluronic TR-702 (manufactured by Asahi Denka Kogyo Co.)was added to the solution, which was thoroughly stirred.

Preparation of Solution (E)

While stirring, 30 parts of toluene was added to 64 parts of anultraviolet ray curable resin dipentaerythritol hexaacrylate (KAYARADDPHA, manufactured by Nippon Kayaku Co.), subsequently adding 0.6 partof a photopolymerization initiator Irgacure 184 and 0.05 part of aslipping agent SH-29PA (manufactured by San Nopco Co.), and theresulting mixture was stirred until the photopolymerization initiatorwas completely dissolved.

While thoroughly stirring, 30 parts of the solution (E) was graduallyadded to the solution (D), thereby obtaining an ultraviolet ray curabletype, solar radiation blocking resin composition (16).

Example 14

A resin composition (17) was obtained in the same manner as described inExample 13, except that Adekacol CC-42 (manufactured by Asahi DenkaKogyo Co.) was used as the dispersing agent. Example 15

A resin composition (18) was obtained in the same manner as described inExample 13, except that 40 parts of the solution (E) was used.

Comparative Example 8

3.5 parts of Pluronic TR-702 as a dispersing agent is added to 50 partsof methanol solution containing 40% of sol of zinc antimonate anhydrideprepared by dispersing in toluene and having a particle size of 0.1 μmor less, and the mixture is thoroughly stirred. Thereafter, a resincomposition (19) was obtained by adding 30 parts of methanol solutioncontaining 30% of a butyral resin Eslec BX-L (manufactured by SekisuiChemical Co.) as a binder.

Preparation of Coating Film

Each of the resin compositions obtained in Examples 13 to 15 andComparative Example 8 was coated on a transparent polyester film of 50μm in thickness using a coating bar to a solid content thickness of 4.1μm dried with hot air to evaporate the solvent and then, in the case ofthe resin composition (16) to resin composition (18), cured by exposingit to ultraviolet rays with a high pressure mercury lamp of 80 W/cm at aconveyor speed of 20 m/min. to obtain the coating film of interest. Inthe case of the resin composition (19), it was used as the coated filmsample after coated and dried by hot air.

Also, to be used as a reference, the transparent polyester film of 50microns in thickness without any coating was subjected to the test.Characteristic properties of the obtained films are shown in Table 4,and their spectral characteristics are shown in FIG. 5.

                  TABLE 4                                                         ______________________________________                                                  Characteristics values when coated                                            on transparent PET film                                                                           Visible Absorp-                                                      Pencil   light   tion ratio                                                   hardness transmittance                                                                         of solar                                          Transparency                                                                             (surface)                                                                              (%)     radiation                               ______________________________________                                        Composition                                                                   16        transparent                                                                              2 H      80.0    0.27                                    17        transparent                                                                              2 H      80.0    0.27                                    18        transparent                                                                              2 H      84.0    0.20                                    19        transparent                                                                              B or less                                                                              78.0    0.30                                    Transparent                                                                             transparent                                                                              B or less                                                                              88.9    0.01                                    polyester film                                                                ______________________________________                                         Visible light transmittance was measured in accordance with the procedure     of JIS A 5759.                                                                Absorption ratio of solar radiation was measured in accordance with the       procedure of JIS R 3106.                                                      (Absorption ratio of solar radiation having larger value means superior       solar radiation blocking efficiency.)                                    

Example 16

A container equipped with a stirrer was charged with 50 parts of atoluene dispersion containing 50% of ATO having a primary particle sizeof 0.1 μm or less, and 6 parts of a toluene solution containing 3% of adispersing agent Floren AF-405 (a polycarboxylic acid base dispersingagent manufactured by Kyoei-sha Yushi Co.) was added to the dispersionwhich was thoroughly stirred. While continuing the stirring, in this wasdissolved 7 parts of a polyester resin Bylon 24SS by adding it in smallportions. Subsequently, 12.5 parts of toluene and 22.5 parts of anultraviolet ray curable type monomer of dipentaerythritol hexaacrylatewere added thereto and dissolved therein and then 2 parts of aphotopolymerization initiator Irgacure 184 was dissolved in theresulting solution, thereby obtaining an ultraviolet ray curable typesolar radiation blocking paint. The thus obtained ultraviolet raycurable type solar radiation blocking paint was coated on the surfaceopposite to the surface of a deposited film having a visible lighttransmittance of 56%, prepared by depositing aluminum on a transparentpolyester film of 50μ in thickness, using a wire bar in such an amountthat the applied amount of the solid content became 6.7 g/m². This wasdried with hot air of 80° C. to evaporate the solvent and then exposedto ultraviolet light of a high pressure mercury lamp of 80 W/cm at aconveyor speed of 20 m/min to effect polymerization curing of the paintfilm, thereby obtaining the solar radiation blocking coating film ofinterest.

Example 17

A solar radiation blocking paint was obtained in the same manner asdescribed in Example 16, except that the same amount of zinc antimonateanhydride gel was used in stead of ATO. The thus obtained solarradiation blocking paint was coated on the surface of a deposition filmhaving a visible light transmittance of 56%, which has been prepared bydepositing aluminum on a transparent polyester film of 25μ in thickness,using a wire bar in such an amount that the applied amount of the solidcontent became 6.7 g/m². This was dried with hot air of 80° C. toevaporate the solvent and then exposed to ultraviolet light of a highpressure mercury lamp of 80 W/cm at a conveyor speed of 20 m/min toeffect polymerization curing of the paint film, thereby obtaining thesolar radiation blocking coating film of interest.

Also, to be used as reference, the deposition film itself used inExample 16 and a commercially available film for car which has beencolored in black with an organic pigment were subjected to the tests.Characteristic properties of the thus obtained films are shown in Table5.

                  TABLE 5                                                         ______________________________________                                                 Characteristics values when coated                                            on transparent PET film                                                                    Absorption ratio                                                 Visible light                                                                              of solar     Scratch                                             transmittance %                                                                            radiation    resistance                                 ______________________________________                                        Example 16                                                                             50.11        0.39         O                                          Example 17                                                                             49.87        0.40         O                                          Deposition film                                                                        56.08        0.29         X                                          Colored film                                                                           21.02        0.35         X                                          ______________________________________                                         Visible light transmittance was measured in accordance with the procedure     of JIS A 5759.                                                                Absorption ratio of solar radiation was measured in accordance with the       procedure of JIS R 3106.                                                      (Absorption ratio of solar radiation having larger value means superior       solar radiation blocking efficiency.)                                         Scratch resistance was measured using steel wool # 0000 under a load of       200 g with 20 reciprocals.                                                    O: completely no scratches                                                    X: presence of scratches                                                 

INDUSTRIAL APPLICABILITY

The active radiation ray curable type, solar radiation blocking risincomposition of the present invention has high transmittance at thevisible light region, is transparent and can be formed easily into acoated film having excellent scratch resistance by the irradiation ofactive energy rays, so that it can be applied most suitably to buildingwindows, car windows and the like as a solar radiation blocking film.

What is claimed is:
 1. A solar radiation blocking resin compositioncurable with active radiation rays, which comprises (1) fine particlesof zinc antimonate anhydride having solar radiation absorption abilitywhich are prepared in such a form that they are dispersed in organicsolvents and have a primary particle size of 0.5 μm or less, (2) anonionic surface active agent having weak cationic activity and (3) abinder containing an active radiation ray polymerizable (meth)acrylatehaving a (meth)acryloyl group as an essential binder.
 2. A film in whichthe resin composition of claim 1 is coated on a film base.
 3. The filmaccording to claim 2 wherein the film base is a transparent or coloredfilm of polyester, polycarbonate or polyurethane, polyvinyl chloride orpoly(meth)acryl or one of these films on which aluminum is deposited.